CN103961725B - Magnetic resonance imaging material and preparation method thereof - Google Patents
Magnetic resonance imaging material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a magnetic resonance imaging material and a preparation method thereof. The magnetic resonance imaging material is Prussian blue doped with paramagnetic metal ions, which can be Cr<3+>, Ce<3+>, Pr<3+>, Nd<3+>, Pm<3+>, Sm<3+>, Eu<3+>, Tb<3+>, Dy<3+>, Ho<3+>, Er<3+>, Tm<3+>, Yb<3+>, Cr<2+>, Co<2+>, Ni<2+>, Cu<2+>, or Eu<2+>. The magnetic resonance imaging material containing the paramagnetic metal ions has stable performance, if the material is placed in hydrochloric acid with pH of 1, normal saline and pure water for 24h, the solution has no significant color change, and is clear and transparent. In the hydrochloric acid with pH of 1, normal saline and water, the content of free metals in the solution is determined to be only several PPM. With good stability, difficult decomposition and ionization, low toxicity, especially stable existence in strong acid solution without decomposition, the magnetic resonance imaging material can be used as injection and oral administration magnetic resonance contrast agents.
Description
Technical field
The present invention relates to mr imaging technique field, more particularly to a kind of magnetic resonance radiography material and its preparation side
Method.
Background technology
Magnetic resonance radiography material is the compound that a class contains one or more paramagnetic metal ions.These compounds can
To change the relaxation time T of in-vivo tissue1Or T2, increase the contrast between normal structure and organ and pathological tissues and organ
Plus, so as to reach the purpose of medical diagnosiss.
At present, several ions are widely used on magnetic resonance contrast agent, for example：Some commercialization magnetic resonance radiographies
Contain Fe in agent2+, Fe3+, Mn2+Or Gd3+.Other metal ions seldom can be made as magnetic resonance due to the unstability in structure
Shadow agent is used.Because these metals separate out in vivo, there is very strong toxicity mostly, and be difficult to be metabolized, so danger
Evil is very big.
Prussian blue is a kind of constitutionally stable coordination compound, contains [Fe (CN) in structure6]4-, can be with other metals
Constitutionally stable coordination compound is formed, water insoluble and organic solvent has less Ksp, is not easily decomposed in vivo, it is difficult to free
Go out metal ion, so toxic and side effects are relatively low, this architectural characteristic so that this kind of compound is suitable as magnetic resonance radiography material
Material.
The content of the invention
Based on this, low magnetic resonance radiography material of a kind of Stability Analysis of Structures, toxicity and preparation method thereof is now provided.
A kind of magnetic resonance radiography material, the magnetic resonance radiography material are the Prussia doped with paramagnetic metal ion
Indigo plant, wherein, the paramagnetic metal ion is Cr3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Tb3+、Dy3+、Ho3+、Er3+、
Tm3+、Yb3+、Cr2+、Co2+、Ni2+、Cu2+Or Eu2+。
Wherein in one embodiment, the chemical formula of the magnetic resonance radiography material is A3x[DIII yFeIII 1-y](4-x)[FeII
(CN)6]3·nH2O；
Wherein, A is Li+, Na+, K+、Rb+、Cs+、NH4 +Or Tl+, 0≤x≤1,0<Y≤1, n=1 ~ 16；
D is Cr3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+Or Yb3+。
Wherein in one embodiment, the chemical formula of the magnetic resonance radiography material is A3x[EII yFeIII (3-2y)/3](4-x)
[FeII(CN)6]3·nH2O；
Wherein, A is Li+, Na+, K+、Rb+、Cs+、NH4 +Or Tl+, 0≤x≤1,0<Y≤1, n=1 ~ 16；
E is Cr2+、Co2+、Ni2+、Cu2+Or Eu2+。
A kind of preparation method of magnetic resonance radiography material, comprises the following steps：
The A that concentration is 0.1mmol/L ~ 2000mmol/L is prepared respectively4[FeII(CN)6] aqueous solution, concentration be 0.1mmol/
The soluble iron saline solution of L ~ 2000mmol/L and the solubility paramagnetic metal that concentration is 0.1mmol/L ~ 2000mmol/L
Saline solution, wherein, A is Li+、Na+、K+、Rb+、Cs+、NH4 +Or Tl+, contain in the solubility paramagnetic metal saline solution
Paramagnetic metal ion, the paramagnetic metal ion are Cr3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Tb3+、Dy3+、Ho3 +、Er3+、Tm3+Or Yb3+、Cr2+、Co2+、Ni2+、Cu2+Or Eu2+；And
By the A4[FeII(CN)6] aqueous solution and the soluble iron saline solution and the solubility paramagnetic metal
Saline solution mix homogeneously, controlling reaction temperature are 0 ~ 100 DEG C, and impurity is removed after fully reacting, and obtain magnetic resonance and make after being dried
Shadow material, wherein, the magnetic resonance radiography material is doped with the Prussian blue of paramagnetic metal ion.
Solubility paramagnetic metal salt wherein in one embodiment, in the solubility paramagnetic metal saline solution
For at least one in the chloride of the paramagnetic metal ion, nitrate and carbonate.
Wherein in one embodiment, the soluble ferric iron salt in the soluble iron saline solution be anhydrous ferric chloride, six
At least one in Ferric Chloride Hydrated, ferric nitrate, iron sulfate, iron acetate, ferric citrate and ferrous gluconate.
Wherein in one embodiment, the removing impurity step includes：Using the method for centrifugation, dialysis or ultrafiltration, remove
Remove unreacted raw material and byproduct of reaction.
Wherein in one embodiment, comprise the following steps：
The A that concentration is 0.1mmol/L ~ 2000mmol/L is prepared respectively4[FeII(CN)6] aqueous solution, concentration be 0.1mmol/
The soluble iron saline solution of L ~ 2000mmol/L and the first solubility paramagnetism that concentration is 0.1mmol/L ~ 2000mmol/L
Aqueous metal salt, wherein, A is Li+、Na+、K+、Rb+、Cs+、NH4 +Or Tl+, the first solubility paramagnetic metal salt is water-soluble
Contain paramagnetic metal ion D in liquid, D is Cr3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3 +Or Yb3+；And
By the A4[FeII(CN)6] aqueous solution and the soluble iron saline solution and the first solubility paramagnetism
Aqueous metal salt mix homogeneously, controlling reaction temperature are 0 ~ 100 DEG C, and impurity is removed after fully reacting, and obtain chemistry after being dried
Formula is A3x[DIII yFeIII 1-y](4-x)[FeII(CN)6]3·nH2The magnetic resonance radiography material of O, wherein, 0≤x≤1,0<Y≤1, n=
1~16。
The first solubility paramagnetic wherein in one embodiment, in the first solubility paramagnetic metal saline solution
Property slaine be the chloride of paramagnetic metal ion D, at least one in nitrate and carbonate.
Wherein in one embodiment, comprise the following steps：
The A that concentration is 0.1mmol/L ~ 2000mmol/L is prepared respectively4[FeII(CN)6] aqueous solution, concentration be 0.1mmol/
The soluble iron saline solution of L ~ 2000mmol/L and the second solubility paramagnetism that concentration is 0.1mmol/L ~ 2000mmol/L
Aqueous metal salt, wherein, A is Li+、Na+、K+、Rb+、Cs+、NH4 +Or Tl+, the second solubility paramagnetic metal salt is water-soluble
Contain paramagnetic metal ion E in liquid, E is Cr2+、Co2+、Ni2+、Cu2+Or Eu2+；And
By the A4[FeII(CN)6] aqueous solution and the soluble iron saline solution and the second solubility paramagnetism
Aqueous metal salt mix homogeneously, controlling reaction temperature are 0 ~ 100 DEG C, and impurity is removed after fully reacting, and obtain chemistry after being dried
Formula is A3x[EII yFeIII (3-2y)/3](4-x)[FeII(CN)6]3·nH2The magnetic resonance radiography material of O, wherein, 0≤x≤1,0<Y≤1,
n=1~16。
The above-mentioned magnetic resonance radiography material containing paramagnetic metal ion, stable performance, such as in the hydrochloric acid of pH=1, physiology salt
After placing 24 hours in water and pure water, solution colour without significant change, clear, the tenor dissociated in determining solution,
All be only several PPM in the hydrochloric acid of pH=1, in normal saline and in water, good stability, be not easily decomposed and ionize, toxicity it is low,
Particularly in strong acid solution can stable existence and do not decompose, can as injection and oral magnetic resonance contrast agent use.
Description of the drawings
Fig. 1 is the KYb prepared by embodiment 1III 0.1FeIII 0.9[FeII(CN)6]·4H2Prepared by O, embodiment 2
KDyIII 0.1FeIII 0.9[FeII(CN)6]·4H2KCo prepared by O, embodiment 3IIFeIII 1/3[FeII(CN)6]·4H2O, enforcement
KCu prepared by example 4IIFeIII 1/3[FeII(CN)6]·4H2The x-ray diffraction pattern of O magnetic resonance radiography materials；
Fig. 2 is Prussian blue crystal structure figure；
Fig. 3 is stability experiment result；
Fig. 4 is the KYb prepared by embodiment 1III 0.1FeIII 0.9[FeII(CN)6]·4H2O relaxation rate realities under 1.5T magnetic fields
Test result；
Fig. 5 is the KDy prepared by embodiment 2III 0.1FeIII 0.9[FeII(CN)6]·4H2O relaxation rate realities under 1.5T magnetic fields
Test result；
Fig. 6 is the KCo prepared by embodiment 3IIFeIII 1/3[FeII(CN)6]·4H2O relaxation rate experiments under 1.5T magnetic fields
As a result；
Fig. 7 is the KCu prepared by embodiment 4IIFeIII 1/3[FeII(CN)6]·4H2O relaxation rate experiments under 1.5T magnetic fields
As a result；
Fig. 8 is the KYb prepared by embodiment 1III 0.1FeIII 0.9[FeII(CN)6]·4H2The cytotoxicity experiment result of O；
Fig. 9 is the KYb for preparing in embodiment 1III 0.1FeIII 0.9[FeII(CN)6]·4H2The external imaging experiment result of O.
Specific embodiment
It is understandable to enable the above objects, features and advantages of the present invention to become apparent from, below to concrete reality of the invention
The mode of applying is described in detail.Elaborate many details in order to fully understand the present invention in the following description.But
The present invention can be implemented with being much different from alternate manner described here, and those skilled in the art can be without prejudice to this
Similar improvement is done in the case of bright intension, therefore the present invention is not embodied as being limited by following public.
The magnetic resonance radiography material of one embodiment, magnetic resonance radiography material are the Pu Lu doped with paramagnetic metal ion
Scholar is blue, wherein, paramagnetic metal ion is Cr3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3 +、Yb3+、Cr2+、Co2+、Ni2+、Cu2+Or Eu2+。
Above-mentioned magnetic resonance radiography material can have（Ⅰ）Or（Ⅱ）The chemical formula of structure：
A3x[DIII yFeIII 1-y](4-x)[FeII(CN)6]3·nH2O（Ⅰ）
A3x[EII yFeIII (3-2y)/3](4-x)[FeII(CN)6]3·nH2O（Ⅱ）
Wherein, A is Li+, Na+, K+、Rb+、Cs+、NH4 +Or Tl+, 0≤x≤1,0<Y≤1, n=1 ~ 16；
D is Cr3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+Or Yb3+；
E is Cr2+、Co2+、Ni2+、Cu2+Or Eu2+。
The above-mentioned magnetic resonance radiography material containing paramagnetic metal ion, stable performance, such as in the hydrochloric acid of pH=1, physiology salt
After placing 24 hours in water and pure water, solution colour without significant change, clear, the tenor dissociated in determining solution,
All be only several PPM in the hydrochloric acid of pH=1, in normal saline and in water, good stability, be not easily decomposed and ionize, toxicity it is low,
Particularly in strong acid solution can stable existence and do not decompose, can as injection and oral magnetic resonance contrast agent use.
The preparation method of above-mentioned magnetic resonance radiography material, comprises the following steps：
Step one, prepare respectively concentration be 0.1mmol/L ~ 2000mmol/L A4[FeII(CN)6] aqueous solution, concentration is
The soluble iron saline solution of 0.1mmol/L ~ 2000mmol/L and concentration are suitable for the solubility of 0.1mmol/L ~ 2000mmol/L
Magnetic metal saline solution, wherein, A is Li+、Na+、K+、Rb+、Cs+、NH4 +Or Tl+, in solubility paramagnetic metal saline solution
Containing paramagnetic metal ion, paramagnetic metal ion is Cr3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Tb3+、Dy3+、Ho3 +、Er3+、Tm3+Or Yb3+、Cr2+、Co2+、Ni2+、Cu2+Or Eu2+。
Wherein, the soluble ferric iron salt in soluble iron saline solution can be soluble ferric iron salt commonly used in the art, or
Be by insoluble iron salt through soda acid oxidation etc. reaction generate soluble ferric iron salt, preferably anhydrous ferric chloride, ferric chloride hexahydrate,
At least one in ferric nitrate, iron sulfate, iron acetate, ferric citrate and ferrous gluconate.
Solubility paramagnetic metal salt in solubility paramagnetic metal saline solution can be commonly used in the art solvable
Property paramagnetic metal salt, or insoluble paramagnetic metal salt is generated into solubility paramagnetism gold through reactions such as soda acid oxidations
Category salt, the preferably at least one in the chloride of paramagnetic metal ion, nitrate and carbonate.
Step 2, by A4[FeII(CN)6] aqueous solution is water-soluble with soluble iron saline solution and solubility paramagnetic metal salt
Liquid mix homogeneously, controlling reaction temperature are 0 ~ 100 DEG C, and impurity is removed after fully reacting, and obtain magnetic resonance radiography material after being dried,
Wherein, magnetic resonance radiography material is doped with the Prussian blue of paramagnetic metal ion.
In the step, A4[FeII(CN)6] aqueous solution is water-soluble with soluble iron saline solution and solubility paramagnetic metal salt
Liquid fully reacts, generate magnetic resonance radiography material, wherein paramagnetic metal ion part replace it is Prussian blue in Fe3+。
The purification process that impurity step can select centrifugation, dialysis or ultrafiltration is removed, unreacted raw material and reaction is removed
By-product.
Specifically, A3x[DIII yFeIII 1-y](4-x)[FeII(CN)6]3·nH2The preparation method of O magnetic resonance radiography materials, bag
Include following steps：
Step one, prepare respectively concentration be 0.1mmol/L ~ 2000mmol/L A4[FeII(CN)6] aqueous solution, concentration is
The soluble iron saline solution of 0.1mmol/L ~ 2000mmol/L and concentration are first solvable for 0.1mmol/L ~ 2000mmol/L's
Property paramagnetic metal saline solution, wherein, A is Li+、Na+、K+、Rb+、Cs+、NH4 +Or Tl+, the first solubility paramagnetic metal salt
Contain paramagnetic metal ion D in aqueous solution, D is Cr3+、Ce3+、Pr3+、Nd3+、Pm3+、Sm3+、Eu3+、Tb3+、Dy3+、Ho3+、Er3 +、Tm3+Or Yb3+。
The first solubility paramagnetic metal salt in first solubility paramagnetic metal saline solution can be paramagnetic metal
At least one in the chloride of ion D, nitrate and carbonate.
Step 2, by A4[FeII(CN)6] aqueous solution and soluble iron saline solution and the first solubility paramagnetic metal salt
Aqueous solution is uniform, and controlling reaction temperature is 0 ~ 100 DEG C, and impurity is removed after fully reacting, and obtains chemical formula for A after being dried3x
[DIII yFeIII 1-y](4-x)[FeII(CN)6]3·nH2The magnetic resonance radiography material of O, wherein, 0≤x≤1,0<Y≤1, n=1 ~ 16.
A3x[EII yFeIII (3-2y)/3](4-x)[FeII(CN)6]3·nH2The preparation method of O magnetic resonance radiography materials, including it is following
Step：
Step one, prepare respectively concentration be 0.1mmol/L ~ 2000mmol/L A4[FeII(CN)6] aqueous solution, concentration is
The soluble iron saline solution of 0.1mmol/L ~ 2000mmol/L and the second solubility that concentration is 0.1mmol/L2000mmol/L
Paramagnetic metal saline solution, wherein, A is Li+、Na+、K+、Rb+、Cs+、NH4 +Or Tl+, the second solubility paramagnetic metal saline
Contain paramagnetic metal ion E in solution, E is Cr2+、Co2+、Ni2+、Cu2+Or Eu2+。
The second solubility paramagnetic metal salt in second solubility paramagnetic metal saline solution be paramagnetic metal from
At least one in the chloride of sub- E, nitrate and carbonate.
Step 2, by A4[FeII(CN)6] aqueous solution and soluble iron saline solution and the second solubility paramagnetic metal salt
Aqueous solution is uniform, and controlling reaction temperature is 0 ~ 100 DEG C, and impurity is removed after fully reacting, and obtains chemical formula for A after being dried3x
[EII yFeIII (3-2y)/3](4-x)[FeII(CN)6]3·nH2The magnetic resonance radiography material of O, wherein, 0≤x≤1,0<Y≤1, n=1 ~
16。
The preparation method process is simple of above-mentioned magnetic resonance radiography material, raw material are easy to get.Obtained magnetic resonance radiography material with
Conventional magnetic resonance radiography material is compared, and relaxation rate is higher, and contrasting effects are preferable.
Below in conjunction with the accompanying drawings and specific embodiment is further elaborated to magnetic resonance radiography material and preparation method thereof.
Embodiment 1
Weigh the K of 4.224g4[FeII(CN)6]·3H2O is dissolved in 1000mL water, obtains the K of 10mmol/L4[FeII
(CN)6] aqueous solution, obtain solution C；
By 2.433g FeCl3·6H2O is dissolved in 900mL water, stirring, obtains the ferric chloride solution of 10mmol/L；
By 0.388g YbCl3·6H2O is dissolved in 100mL water, stirring, obtains the Ytterbium trichloride solution of 10mmol/L；
Above-mentioned iron chloride and Ytterbium trichloride solution are mixed, then in solution C, mixing speed is 1000rpm to fast drop,
Reaction temperature is 15 DEG C, and the response time is 60min, reacted solution is dialysed, is then centrifuged for, and speed is
10000rpm, time are 10min, take out precipitation, it is freeze-dried after, obtain magnetic resonance radiography material.X-ray diffraction pattern is such as
Shown in Fig. 1, its structure with it is Prussian blue（It is abbreviated as PB）Similar, the position of part Fe is replaced by Yb；The compound is with PB's
Crystal formation（As shown in Figure 2）It is similar, it is cubic system, space group isCell parameter is： Its Elemental analysis data is as follows：K:9.98%, Yb:4.43%, Fe:27.2%, CN:39.9%；Jing thermogravimetrics
Analysis contains 4 water of crystallization in understanding compound, its chemical formula is KYbIII 0.1FeIII 0.9[FeII(CN)6]·4H2O（It is abbreviated as
YbPB）
Embodiment 2
Weigh the K of 4.224g4[FeII(CN)6]·3H2O is dissolved in 1000mL water, obtains the K of 10mmol/L4[FeII
(CN)6] aqueous solution, obtain solution C；
By 2.433g FeCl3·6H2O is dissolved in 900mL water, stirring, obtains the ferric chloride solution of 10mmol/L；
By 0.377g DyCl3·6H2O is dissolved in 100mL water, stirring, obtains the Ytterbium trichloride solution of 10mmol/L；
Above-mentioned iron chloride and dysprosium chloride solution are mixed, then in solution C, mixing speed is 800rpm to fast drop,
Reaction temperature is 25 DEG C, and the response time is 40min, reacted solution is dialysed, is then centrifuged for, and speed is 8000rpm,
Time is 5min, takes out precipitation, after drying, that is, obtains magnetic resonance radiography material.X-ray diffraction pattern is as shown in figure 1, its knot
Structure with it is Prussian blue（It is abbreviated as PB）Similar, the position of part Fe is replaced by Dy；The crystal formation of the compound and PB（Such as Fig. 2 institutes
Show）It is similar, it is cubic system, space group isCell parameter is：
Its Elemental analysis data is as follows：K:10.01%, Dy:4.16%, Fe:27.3%, CN:40.4%；During Jing thermogravimetric analysiss understand compound
Containing 4 water of crystallization.Its chemical formula is KDyIII 0.1FeIII 0.9[FeII(CN)6]·4H2O（It is abbreviated as DyPB）.
Embodiment 3
Weigh the K of 4.224g4[FeII(CN)6]·3H2O is dissolved in 1000mL water, obtains the K of 10mmol/L4[FeII
(CN)6] aqueous solution, obtain solution C；
By 0.891g FeCl3·6H2O is dissolved in 900mL water, stirring, obtains the ferric chloride solution of 3.67mmol/L；
By 2.379g CoCl2·6H2O is dissolved in 100mL water, stirring, obtains the cobalt chloride solution of 100mmol/L；
Above-mentioned iron chloride and cobalt chloride solution are mixed, then in solution C, mixing speed is 800rpm to fast drop,
Reaction temperature is 35 DEG C, and the response time is 30min, and by reacted solution centrifugal, speed is 6000rpm, and the time is 10min,
Precipitation is taken out, after drying, magnetic resonance radiography material is obtained.X-ray diffraction as shown in figure 1, its structure is similar to Prussian blue,
The position of part Fe is replaced by Co；The compound is cubic system, and space group isCell parameter is： Its Elemental analysis data is as follows：K:9.7%, Co:14.7%, Fe:18.6%, CN:
38.9%, meet with molecular formula；Jing thermogravimetric analysiss contain 4 water of crystallization in understanding compound.Its chemical formula is：KCoIIFeIII 1/3
[FeII(CN)6]·4H2O（It is abbreviated as CoPB）
Embodiment 4
Weigh the K of 4.224g4[FeII(CN)6]·3H2O is dissolved in 1000mL water, obtains the K of 10mmol/L4[FeII
(CN)6] aqueous solution, obtain solution C；
By 0.891g FeCl3·6H2O is dissolved in 900mL water, stirring, obtains the ferric chloride solution of 3.7mmol/L；
By 2.5g CuSO4·5H2O is dissolved in 100mL water, stirring, obtains the cobalt chloride solution of 100mmol/L；
Above-mentioned iron sulfate and copper-bath are mixed, then in solution C, mixing speed is 600rpm to fast drop,
Reaction temperature is 30 DEG C, and the response time is 30min, and by reacted solution centrifugal, speed is 4000rpm, and the time is 10min,
Precipitation is taken out, after drying, magnetic resonance radiography material is obtained.X-ray diffraction as shown in figure 1, its structure is similar to Prussian blue,
The position of part Fe is replaced by Cu, forms solid solution；The compound is cubic system, and space group isCell parameter
For： Elementary analysiss understand：K:10.4%, Cu:8.5%, Fe:20%, CN:41.8%,
Jing thermogravimetric analysiss contain 4 water of crystallization in understanding compound, the magnetic resonance radiography materials chemistry formula is KCuIIFeIII 1/3[FeII
(CN)6]·4H2O（CuPB）.
Stability experiment
Obtained YbPB magnetic resonance radiography materials in embodiment 1 are respectively put into into hydrochloric acid, normal saline and the pure water of pH=1
In, after placing 24 hours, observe its steadiness as follows：
Solution colour determines CN in solution without significant change, clear-And Yb3+Content, in the hydrochloric acid of pH=1, life
All it is only several PPM in reason saline and in pure water, as shown in figure 3, CN-Content is well below the amount in smoking human body, Yb3+Content
Also be far smaller than toxic dose, illustrate the stability of YbPB very well, particularly in acid can stable existence, do not decompose, and malicious
Property is little, can not only be also used as oral administration nanometer magnetic resonance radiography material as ejection preparation.
Relaxation rate is tested
Relaxation rate is the important indicator for evaluating magnetic resonance radiography material contrasting effects, and in Example 1 ~ 4, obtained magnetic is common
The radiography material that shakes is some, is diluted to the solution of variable concentrations respectively, takes 500 μ L and is put in sample cell, sample cell is put into
15min is heated in 37 DEG C of water-baths, is then placed in instrument probe after 5min, starting measurement, magnetic field intensity is 1.5T, meanwhile, we
Take commercially available prod Magnevist（Gd-DTPA）, as reference.
As shown in Figure 4, Figure 5, Figure 6 and Figure 7, under 1.5T magnetic fields, difference contains paramagnetic metal ion to relaxation rate result
The relaxation rate result of magnetic resonance radiography material is as shown in table 1.
The relaxation rate of the 1 different magnetic resonance radiography materials containing paramagnetic metal ion of table
| Contrast agent | Radiography material | R1(mM-1s-1) | Magnetic field intensity |
| Embodiment 1 | YbPB | 15.60 | 1.5T |
| Embodiment 2 | DyPB | 12.02 | 1.5T |
| Embodiment 3 | CoPB | 12.02 | 1.5T |
| Embodiment 4 | CuPB | 7.50 | 1.5T |
| With reference to experiment | Gd-DTPA | 3.27 | 1.5T |
As can be seen from the above table, the magnetic resonance radiography material containing paramagnetic metal ion, external relaxation rate R1It is very high, be
3 ~ 5 times of presently commercially available commodity Magnevist, illustrate the little dosage of such substance migration, i.e., can reach diagnostic purpose, its
Toxicity also significantly can be reduced.
Toxicity test
YbPB obtained in embodiment 1 is configured to into variable concentrations, is respectively put in cell culture fluid, carry out cell culture,
Time is 12 hours and 24 hours, as a result as shown in Figure 8.
As shown in Figure 8, at various concentrations, find cell have any exception, illustrate the magnetic resonance radiography material without
Obvious toxic-side effects.
External imaging experiment
Be 0.1 to concentration, 0.3, the YbPB solution of 0.5mmol/L carry out external imaging experiment, as a result as shown in Figure 9.
As shown in Figure 9, with the increase of YbPB solution concentrations, imaging effect substantially increases, and in YbPB solution concentrations
For 0.3mmol/L when, imaging effect preferably, illustrate YbPB magnetic resonance radiographies material when usage amount is less, can just reach preferable
Imaging effect, reach diagnostic purpose.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the guarantor of the present invention
Shield scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (2)
1. a kind of magnetic resonance radiography material, it is characterised in that the magnetic resonance radiography material is doped with paramagnetic metal ion
It is Prussian blue；
The chemical formula of the magnetic resonance radiography material is KYbIII 0.1FeIII 0.9[FeII(CN)6]·4H2O。
2. a kind of preparation method of magnetic resonance radiography material, it is characterised in that comprise the following steps：
Weigh the K of 4.224g4[FeII(CN)6]·3H2O is dissolved in 1000mL water, obtains the K of 10mmol/L4[FeII(CN)6]
Aqueous solution, obtains solution C；
By 2.433g FeCl3·6H2O is dissolved in 900mL water, stirring, obtains the ferric chloride solution of 10mmol/L；
By 0.388g YbCl3·6H2O is dissolved in 100mL water, stirring, obtains the Ytterbium trichloride solution of 10mmol/L；
Above-mentioned iron chloride and Ytterbium trichloride solution are mixed, then in solution C, mixing speed is 1000rpm to fast drop, reaction
Temperature is 15 DEG C, and the response time is 60min, reacted solution is dialysed, is then centrifuged for, and speed is 10000rpm, when
Between be 10min, take out precipitation, it is freeze-dried after, obtain magnetic resonance radiography material.
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